CN106537553B - The patterning apparatus of self-assembled monolayer, the patterning method of light irradiation device and self-assembled monolayer - Google Patents

The patterning apparatus of self-assembled monolayer, the patterning method of light irradiation device and self-assembled monolayer Download PDF

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CN106537553B
CN106537553B CN201580038998.7A CN201580038998A CN106537553B CN 106537553 B CN106537553 B CN 106537553B CN 201580038998 A CN201580038998 A CN 201580038998A CN 106537553 B CN106537553 B CN 106537553B
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light
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vuv
vacuum
self
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CN106537553A (en
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大和田树志
铃木信二
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Ushio Denki KK
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Ushio Denki KK
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/84—Lamps with discharge constricted by high pressure
    • H01J61/90—Lamps suitable only for intermittent operation, e.g. flash lamp
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
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    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/165—Monolayers, e.g. Langmuir-Blodgett
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70008—Production of exposure light, i.e. light sources
    • G03F7/70016—Production of exposure light, i.e. light sources by discharge lamps
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    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70008—Production of exposure light, i.e. light sources
    • G03F7/70041—Production of exposure light, i.e. light sources by pulsed sources, e.g. multiplexing, pulse duration, interval control or intensity control
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70058—Mask illumination systems
    • G03F7/7015—Details of optical elements
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70216—Mask projection systems
    • G03F7/7035—Proximity or contact printers
    • G—PHYSICS
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70425—Imaging strategies, e.g. for increasing throughput or resolution, printing product fields larger than the image field or compensating lithography- or non-lithography errors, e.g. proximity correction, mix-and-match, stitching or double patterning
    • G03F7/70466—Multiple exposures, e.g. combination of fine and coarse exposures, double patterning or multiple exposures for printing a single feature
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
    • G03F7/70908—Hygiene, e.g. preventing apparatus pollution, mitigating effect of pollution or removing pollutants from apparatus
    • G03F7/70933—Purge, e.g. exchanging fluid or gas to remove pollutants
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    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/12—Selection of substances for gas fillings; Specified operating pressure or temperature
    • H01J61/16—Selection of substances for gas fillings; Specified operating pressure or temperature having helium, argon, neon, krypton, or xenon as the principle constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/36—Seals between parts of vessels; Seals for leading-in conductors; Leading-in conductors
    • H01J61/366—Seals for leading-in conductors
    • H01J61/368—Pinched seals or analogous seals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/54—Igniting arrangements, e.g. promoting ionisation for starting
    • H01J61/545—Igniting arrangements, e.g. promoting ionisation for starting using an auxiliary electrode inside the vessel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/84—Lamps with discharge constricted by high pressure
    • H01J61/86—Lamps with discharge constricted by high pressure with discharge additionally constricted by close spacing of electrodes, e.g. for optical projection
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • H—ELECTRICITY
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    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
    • H01S3/22—Gases
    • H01S3/223—Gases the active gas being polyatomic, i.e. containing two or more atoms
    • H01S3/225—Gases the active gas being polyatomic, i.e. containing two or more atoms comprising an excimer or exciplex
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
    • H01S3/22—Gases
    • H01S3/223—Gases the active gas being polyatomic, i.e. containing two or more atoms
    • H01S3/225—Gases the active gas being polyatomic, i.e. containing two or more atoms comprising an excimer or exciplex
    • H01S3/2253—XeCl, i.e. xenon chloride is comprised for lasing around 308 nm
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    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
    • H01S3/22—Gases
    • H01S3/223—Gases the active gas being polyatomic, i.e. containing two or more atoms
    • H01S3/225—Gases the active gas being polyatomic, i.e. containing two or more atoms comprising an excimer or exciplex
    • H01S3/2255—XeF, i.e. xenon fluoride is comprised for lasing around 351 nm
    • H—ELECTRICITY
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    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B41/00—Circuit arrangements or apparatus for igniting or operating discharge lamps
    • H05B41/14—Circuit arrangements
    • H05B41/30—Circuit arrangements in which the lamp is fed by pulses, e.g. flash lamp
    • H05B41/34—Circuit arrangements in which the lamp is fed by pulses, e.g. flash lamp to provide a sequence of flashes

Abstract

It can inhibit to the ozone yield wrapped when having irradiated vacuum-ultraviolet light (VUV light) in oxygen containing atmosphere.Light irradiation device (100) is in wrapping oxygen containing atmosphere, the illumination comprising VUV light is mapped to the self-assembled monolayer (SAM films) being formed on workpiece (W) via the mask (M) for being formed with defined pattern, patterned process thus is carried out to above-mentioned SAM films.The light comprising VUV light for being irradiated to SAM films is pulsed light, and luminous duty ratio is 0.00001 or more and 0.01 or less.

Description

Patterning apparatus, light irradiation device and single point of the self assembly of self-assembled monolayer The patterning method of sub- film
Technical field
The present invention relates to the vacuum-ultraviolet light light supply apparatus of light of the release comprising vacuum-ultraviolet light, the vacuum ultraviolet is installed The light irradiation device of radiant device and the patterning for using the self-assembled monolayer for having the light irradiation device (Patterning) method.
Background technology
In recent years, wavelength is 200nm vacuum ultraviolet below (Vacuum Ultra Violet：VUV) light, which is used in, removes In various fields other than semiconductor exposure.For example, exploitation, which has, does not use the pattern formation process based on photoresist, but Using VUV and mask, directly by self-assembled monolayer (Self-Assembled by light causes chemical reaction Monolayer：SAM films) patterned technology.
For example, being disclosed in non-patent literature 1 can use VUV light to carry out the SAM independent of specific functional group The photo-patterning of film is handled.Specifically, by used, wavelength 172nm when removing the polluter being made of organic matter Excimer lamp be used as exposure light source.It can expect the side for the oxygenolysis removal reaction based on VUV light for being conceived to SAM films Method and be varied SAM films to the micro-machined expansion of light.
In the past as vacuum ultraviolet radiant (hereinafter, also referred to as " VUV light source "), having used has on wavelength 185nm The Cooper-Hewitt lamp of bright line.On the other hand, it is known that in VUV light, particularly wavelength 180nm wave bands below light can be realized The surface of high speed is modified (for example, ashing (Ashing)) etc..Therefore, in recent years, the xenon standard point for the light that wavelength is 172nm will be discharged The example that sub- lamp is used as VUV light source is more.
However, that the above-mentioned lamp in general length of illumination region, i.e. length of illumination of release VUV light is longer.For example, low The length of illumination of medium pressure mercury lamp (USHIO Electric Co., Ltd UL0-6DQ) is 10cm.In addition, for example, built-in xenon excimer lamp Quasi-molecule light unit (USHIO Electric Co., Ltd SUS06) length of illumination also be 10cm.
This VUV light discharged from VUV lamps is because the shape of light-emitting zone is substantially cylindric, so becoming diverging light. In the case of diverging light, it is difficult to carry out projection exposure, but carry out contact exposure, proximity printing.In this case, to The exposure of shone thing is influenced by the diffraction of diverging light, discernmible pattern dimension by line image width for, pole It is limited to 100 μm or so.
In order to realize the miniaturization of pattern line-width, carry out having used the length of illumination as being regarded as point light source abundant The few exposure of the lamp of the up to practical upper sufficient degree of short, vacuum-ultraviolet light intensity, light diffraction.Therefore, as being used in The patterned light source of SAM films considers that length of illumination is used to be 12.5mm or less and discharge the VUV light of sufficient intensity in practicality Flash lamp.By the way that the flash lamp and parabolic mirror is applied in combination, it can realize extraction VUV light and be as parallel The light supply apparatus of light or the light of roughly parallel light.It therefore, can be in SAM in the light irradiation device for being equipped with the light supply apparatus The miniaturization of pattern line-width is realized in the patterning of film.
In addition, as VUV light source, there is also the excimer laser dresses for being used in semiconductor exposure other than above-mentioned lamp It sets.According to the excimer laser exposure device for being equipped with excimer laser apparatus, pattern can be realized in the patterning of SAM films The miniaturization of line width.However, excimer laser apparatus, the price of excimer laser exposure device are high, for COO (Cost Of Ownership viewpoint), other than being in the semiconductor exposure in volume production stage use be and unpractiaca.In other words, Excimer laser apparatus is only limitted to use in the industrial circle to match with COO.
Existing technical literature
Non-patent literature
Non-patent literature 1：Shan Cun wins it, " the light micro Process of organic monomolecular film ", vacuum, Japanese vacuum association, and 2005 Year, volume 48, No. 9, p.506-510
Invention content
Problems to be solved by the invention
However, VUV light is absorbed by oxygen in an atmosphere, it is therefore desirable to use in a vacuum or in inert gas atmosphere.However, It is this not comprising the atmosphere of oxygen in SAM films irradiate VUV light in the case of, the direct of the SAM films based on VUV light can only be carried out It decomposes, pattern rate cannot be improved.
And if VUV light is irradiated to SAM films in air etc. wraps oxygen containing processing atmosphere, the oxygen near SAM film surfaces leads to Crossing VUV irradiations becomes active oxygen, can carry out the direct decomposition of the SAM films based on VUV light, and can also carry out above-mentioned work The oxidative decomposition of property oxygen and SAM films.Moreover, the presence of the oxidative decomposition based on the active oxygen, which becomes, makes SAM films The principal element that pattern rate improves.Therefore, in order to ensure pattern rate, the SAM based on VUV is preferably carried out in an atmosphere The patterning of film.
However, the case where carrying out having used the photo-irradiation treatment of wavelength 200nm VUV lights below to workpiece in an atmosphere Under, generate ozone in light irradiation surface, comprising the space on the surface.
Think that ozone is generated by following chemical reaction.
First, the oxygen molecule in air absorbs ultraviolet light and becomes excitation state.
O2(3Σg-：Ground state)+h ν → O2(3Σu-：Excitation state) ... (1)
Next, the oxygen molecule of excitation state becomes the oxygen atom of excitation state.
O2(3Σu-：Excitation state) → O (3P：Excitation state)+O (1D：Excitation state) ... (2)
Alternatively, the oxygen molecule in air absorbs ultraviolet light, and as the oxygen atom of excitation state.
O2(3Σg-：Ground state)+h ν → O (1D：Excitation state)+O (1D：Excitation state) ... (3)
Then, by the oxygen atom O of excitation state (1D：Excitation state), oxygen molecule and surrounding medium M (nitrogen molecular etc.) Three-body collision generates ozone.
O(1D)+O2+M→O3……(4)
In the case where irradiating VUV light to SAM films and carry out patterned process, it is generally desirable to, as shown in figure 11, pass through The mask pattern of mask M, the VUV light (VUV) from VUV light source 200 be irradiated to the SAM films (SAM) on workpiece W, by VUV The part of light irradiation patterns SAM films by the oxygenolysis removal reaction based on VUV light etc. of SAM films.
However, in the case that VUV in an atmosphere irradiates, ozone O is actually such as generated as shown in Figure 123.By In the ozone O of generation3Service life reach tens seconds, therefore under the VUV light of SAM films oxygenolysis removal reaction while, Also ozone O is generated3With the oxidative decomposition of SAM films (ozone in Figure 11 etches OE).Therefore, the patterning of SAM films is not One is shaped as desirable pattern.That is, it is this bad to occur generating the expansion of etched width, the local defect (etching) of SAM films Situation.
Therefore, the patterned of SAM films is carried out using VUV in air etc. wraps oxygen containing atmosphere, needs to consider The influence of the ozone generated because VUV irradiates.However, in the technology that above-mentioned non-patent literature 1 is recorded, this is not considered completely A bit.
Therefore, problem of the present invention is that, a kind of vacuum-ultraviolet light light in light of the release comprising vacuum-ultraviolet light is provided In source device, the vacuum-ultraviolet light light of the ozone yield when having irradiated vacuum ultraviolet light in wrapping oxygen containing atmosphere can be inhibited Source device, the light irradiation device for being equipped with the vacuum-ultraviolet light light supply apparatus and use have the self assembly of the light irradiation device The patterning method of monomolecular film.
Means for solving the problems
In order to solve the above problems, a mode of vacuum-ultraviolet light light supply apparatus of the invention is, a kind of release includes The vacuum-ultraviolet light light supply apparatus of the light of vacuum-ultraviolet light by pulsed light and is as the above-mentioned light for including vacuum-ultraviolet light Luminous duty ratio is that 0.00001 or more and 0.01 light below is discharged into the oxygen containing atmosphere of packet.Thereby, it is possible to inhibit big The ozone generated when gas etc. wraps release vacuum ultraviolet light in oxygen containing atmosphere, because of the oxygen molecule absorption ultraviolet light in the atmosphere Amount.
In addition, other modes according to the present invention, can also be, above-mentioned luminous duty ratio be 0.0001 or more and 0.001 or less.Thereby, it is possible to the luminescent conditions can relatively easily realize, ozone yield is fully decreased to not have in practicality Problematic degree.
Moreover, other modes according to the present invention, can also be, have：Flash lamp has by vacuum ultraviolet transmitance The luminous tube and configure mutually opposed a pair of electrodes in the luminous tube that material is constituted；And power supply, to above-mentioned sudden strain of a muscle Light lamp supplies electric power.In this way, the light source as light of the release comprising vacuum-ultraviolet light uses flash lamp, therefore can suitably release Pile the light of sufficient above-mentioned condition.
In addition, other modes according to the present invention, can also be, the electrode spacing of above-mentioned a pair of electrodes of above-mentioned flash lamp From for 12.5mm hereinafter, being sealed with the gas comprising xenon in the above-mentioned luminous tube of above-mentioned flash lamp.Flash lamp can as a result, Release length of illumination is as short as that the vacuum-ultraviolet light of the degree of point light source can be regarded as enough.Therefore, which can for example make For used mask, use for carrying out small patterned lamp.
Moreover, a mode of the light irradiation device of the present invention is a kind of light irradiation device, have：Mask, be formed with from The workpiece of assembling monomolecular film discretely configures, and is formed with defined pattern；Any of the above-described kind of vacuum-ultraviolet light light supply apparatus, The light for including vacuum-ultraviolet light is irradiated on above-mentioned workpiece via aforementioned mask；And component is surrounded, it will be from above-mentioned vacuum ultraviolet The light path of radiant device to the above-mentioned light of aforementioned mask is surrounded；The inside of above-mentioned encirclement component is cleaned by inert gas (Purge is removed), is formed with the oxygen containing gas blanket of packet between aforementioned mask and above-mentioned workpiece.
In this way, the enclosure for surrounding the light path from light supply apparatus to mask due to removing (Purge) by inert gas The oxygen of the inside of part, therefore it is capable of the attenuation by absorption of vacuum-ultraviolet light caused by anti-block.In addition, due to from mask to workpiece Between formed and wrap oxygen containing gas blanket, therefore single point of the self assembly based on vacuum-ultraviolet light can be carried out in wrapping oxygen containing atmosphere The patterned process of sub- film (SAM films).Therefore, when irradiating vacuum ultraviolet light to SAM films, the oxygen near SAM film surfaces becomes Active oxygen can carry out the oxidative decomposition of the active oxygen and SAM films.Thereby, it is possible to so that the pattern rate of SAM films is improved.
Moreover, vacuum-ultraviolet light light supply apparatus release pulsed light and be luminous duty ratio be 0.00001 or more and 0.01 light below is as the light comprising vacuum-ultraviolet light.Therefore, it is possible to inhibit to absorb because of the oxygen molecule between mask and workpiece Ultraviolet light and the amount of ozone generated.Therefore, it is possible to inhibit patterned deformation caused by ozone etching, good pattern is realized Change.
In addition, a mode of patterning method for the self-assembled monolayer of the present invention is, via being formed with defined figure The mask of case irradiates the light for including vacuum-ultraviolet light, wherein oxygen containing wrapping to the self-assembled monolayer being formed on workpiece In atmosphere, as the above-mentioned light for including vacuum-ultraviolet light, irradiating pulsed light and be luminous duty ratio be 0.00001 or more And 0.01 light below.
Thereby, it is possible to inhibit ozone yield, and the patterned process of SAM films can be carried out.Therefore, it is possible to inhibit smelly Oxygen etches and realizes good patterning.
Moreover, in the patterning method of above-mentioned self-assembled monolayer, can also be, as above-mentioned purple comprising vacuum The light of outer light, it is 0.0001 or more and 0.001 light below to irradiate above-mentioned luminous duty ratio.Thereby, it is possible to use relatively to hold Change places realization light supply apparatus in the state that ozone yield is fully decreased to the degree that there is no problem in practicality, carry out The patterned process of SAM films.
Invention effect
In the vacuum-ultraviolet light light supply apparatus of the present invention, it can inhibit to discharge vacuum in air etc. wraps oxygen containing atmosphere The amount of the ozone generated when ultraviolet light.Therefore, in the light irradiation device for being equipped with the vacuum-ultraviolet light light supply apparatus, comprising In the patterned process of SAM films in the atmosphere of oxygen, it can inhibit caused by oxidative decomposition of the ozone generated with SAM films Ozone etching, so as to realize good patterning.
If it is those skilled in the art, then should be able to by referring to accompanying drawing and the record of claims, according to Understand the purpose, mode and effect of aforementioned present invention for implementing the mode (detailed description of the invention) of following inventions, and The purpose of the present invention, mode and the effect not described above.
Description of the drawings
Fig. 1 is the figure of the spatial distribution for the light for indicating to discharge from Excimer lamp.
Fig. 2 is the figure for indicating the spatial distribution from the VUV-SFL light discharged.
Fig. 3 is the figure for an example for indicating VUV-SFL.
Fig. 4 is the figure of the variation of the contact angle of SAM films when indicating the light of irradiation Excimer lamp.
Fig. 5 is the figure of the variation of the contact angle of SAM films when indicating the light of irradiation VUV-SFL.
Fig. 6 is the figure for the experimental system for indicating to measure for ozone concentration.
Fig. 7 is the different figures for indicating Excimer lamp and the ozone yield of VUV-SFL.
Fig. 8 is the figure of the definition for illustrating duty ratio.
Fig. 9 is the figure for indicating duty ratio and the relationship of ozone concentration.
Figure 10 is the figure for the configuration example for indicating light irradiation device.
Figure 11 is the figure for the patterning method for indicating SAM films.
Figure 12 is the figure for the example for indicating ozone etching.
Specific implementation mode
Hereinafter, based on attached drawing, embodiments of the present invention will be described.
The present inventors gives birth to investigate because the oxygen molecule in air etc. qi-regulating atmosphere absorbs vacuum-ultraviolet light (VUV light) At ozone production quantity, carried out ozone concentration determination experiment below.
Specifically, the use of release centre wavelength being the Excimer lamp of the VUV light of 172nm and the luminous intensity in the regions VUV Strong VUV flash lamps (VUV short arc flash lamps：VUV-SFL), the VUV light for making to be irradiated into air from the two has been investigated respectively Ozone yield when accumulative exposure is identical.
As the Excimer light irradiation unit of irradiation quasi-molecule light, USHIO Electric Co., Ltd system " Min- has been used Excimer SUS713”.The length of illumination of lamp is 100mm, and the frequency of the power supply supplied electric power to lamp is 140kHz.It will be from the standard The spatial distribution of the light of molecule lamp release indicates in Fig. 1.In addition, in Fig. 1, horizontal axis is wavelength (Wavelength) [nm], The longitudinal axis is relative intensity (Relative Intensity) [%].
On the other hand, as VUV-SFL, following flash lamp has been used：It is configured at by vacuum-ultraviolet light transmission material structure At luminous tube (quartz glass tube etc.) in a pair of electrodes between distance be 12.5mm hereinafter, and in the luminous tube with enclose gas Body pressure 3atm is sealed with the gas comprising xenon.The spatial distribution of the light discharged from the VUV-SFL is indicated in fig. 2.This Outside, in fig. 2, horizontal axis is wavelength [nm], and the longitudinal axis is light splitting activity [μ J/cm2]。
Here, the construction of VUV-SFL is illustrated.
Fig. 3 is the figure of the construction of the double ended type short arc flash lamp for an example for being denoted as VUV-SFL.
As shown in figure 3, VUV-SFL11 has luminous tube 111a.It is close it to be continuously provided with first at the both ends of luminous tube 111a Tube sealing 111b and the second seal pipe 111c.In addition, inserted with glass for sealing pipe 112, the two quilt in the second seal pipe 111c Welding.
Be arranged opposite to each other a pair of electrodes (the first main electrode 113a and the second main electrode 113b) in luminous tube 111a.From Conducting wire (Lead) 114a that one main electrode 113a extends by mechanism supports such as gradual change glass and is sealed in the first seal pipe 111b, And it is exported to its outside.In addition, the conducting wire 114b of the second main electrode 113b by mechanism supports such as gradual change glass and is sealed in Glass for sealing pipe 112, and be exported to its outside.
A pair of start auxiliary electrode 115a in addition, being equipped between main electrode 113a and 113b in luminous tube 111a And 115b.Start the outer lead 117a of inner lead 116a and startup auxiliary electrode 115a of auxiliary electrode 115a second Welding region between seal pipe 111c and glass for sealing pipe 112 is electrically connected via metal foil 118a.Equally, start auxiliary The outer lead 117b of the inner lead 116b of electrode 115b and startup auxiliary electrode 115b is in the second seal pipe 111c and sealing With the welding region between glass tube 112, it is electrically connected via metal foil 118b.
Moreover, being equipped with support element 119 between a pair of of inner lead 116a and 116b, become the support element 119 progress Start the structure of the positioning of auxiliary electrode 115a and 115b.
Conducting wire 114a, 114b and outer lead 117a, 117b are connected to power supply 15.Power supply 15 has savings The capacitor (not shown) of defined energy.Power supply 15 by the capacitor is charged to a pair of electrodes 113a and 113b it Between apply high voltage, and start to a pair supply high voltage pulse conduct between auxiliary electrode 115a and 115b in this state Trigger voltage.Power supply 15 makes to generate arc discharge between a pair of electrodes 113a, 113b as a result, and sudden strain of a muscle is generated in luminous tube 111a Light discharges.In this way, luminous tube 111a discharges pulsed light to outside.
That is, as VUV-SFL used in ozone concentration determination experiment, using a pair of electrodes 113a shown in Fig. 3 and Distance between 113b is 12.5mm or less and is sealed with the gas comprising xenon in luminous tube 111a with enclosed gas pressure 3atm The VUV-SFL of body.As a result, the VUV-SFL can be considered point light source discharge like that comprising length of illumination fully it is short and sufficiently strong The light of the VUV light of degree.
In addition, the VUV-SFL as the release strong VUV light of luminous intensity, can be 12.5mm or less using interelectrode distance, The VUV-SFL that the gas comprising xenon and the enclosed gas pressure are 2atm~8atm is sealed in luminous tube.
As shown in Figure 1 and Figure 2, in Excimer lamp and VUV-SFL, spatial distribution is different.The patterning of SAM films is done The light for going out contribution is that wavelength region is 200nm VUV lights below, therefore in ozone concentration determination experiment, needs to make the wavelength The exposure of light in region is equal, to confirm the difference of ozone yield.
However, Excimer lamp only discharges wavelength 200nm light below as shown in Figure 1, but discharged in VUV-SFL In light, the wavelength components of wavelength 200nm are comprised more than as shown in Figure 2.Therefore, it in VUV-SFL, can not merely measure The illumination of wavelength 200nm light below.
Therefore, the present inventors be conceived to if wavelength region 200nm VUV lights below be irradiated to SAM films, if SAM films Contact angle variation this case, it is contemplated that from standard point of the beginning to SAM films irradiation light until the variation of the contact angle of SAM films is stablized The exposure of shared VUV in the light irradiation amount of sub- lamp, and from starting to SAM films irradiation light to the variation of the contact angle of SAM films The exposure of VUV-SFL until stabilization is equal.Then, the wavelength 200nm light below of VUV-SFL is calculated under the imagination Illumination.Hereinafter, being illustrated to this point.
Fig. 4 is indicated in an atmosphere using above-mentioned Excimer lamp irradiation quasi-molecule light so that the SAM films on workpiece (substrate) The illumination on surface becomes 8.25mW/cm2When, the figure of the variation of the contact angles of SAM films.In addition, here, as SAM films, using 1H, 1H, 2H, 2H- perfluoro capryls trimethoxy silane (FAS13, Wako Pure Chemical Industries, Ltd.'s system).As shown in figure 4, logical Cross 75 seconds light of irradiation so that the variation of the contact angle of SAM films is stablized.Specifically, the contact angle of SAM films is from 58 ° of variations It is 42 °, substantially constant.
Fig. 5 is when indicating to irradiate the pulsed light from VUV-SFL to the SAM films on workpiece in an atmosphere, SAM films connects The figure of the variation of feeler.Rechargeable energy charged to VUV-SFL inputs with 600V, the capacitor of 20 μ F of capacity (that is, 1/2 × 20×10-6×6002=3.6J), so that the VUV-SFL is lighted with 10Hz.As shown in figure 5, by irradiating 120 seconds light so that SAM The variation of the contact angle of film is stablized.Specifically, it is 33 ° that the contact angle of SAM films changes from 58 °, it is substantially constant.
In addition, as shown in Figure 4 and 5, even if the contact angle of SAM films when light irradiation starts is identical, the change of contact angle Change the size of contact angle when stablizing and is mapped to SAM films when the illumination of VUV-SFL is mapped to SAM films and by the illumination of Excimer lamp When it is also different.Think the reason is that, can obviously be learnt according to the spatial distribution of Fig. 1 and Fig. 2, from VUV-SFL discharge light in Wide, the wavelength more discharged from Excimer lamp containing energy ratio is 200nm wavelength components below (VUV), by VUV- When the illumination of SFL is mapped to SAM films, the decomposition based on VUV irradiations of SAM films is further carried out.
As described above, the variation of the contact angle of SAM films reach stablize until time be in the case of VUV-SFL 120 seconds, be 75 seconds in the case of Excimer lamp.It is therefore contemplated that irradiation 120 seconds VUV-SFL light when wavelength 200nm with Under 75 seconds light from Excimer lamp of VUV light exposure and irradiation when VUV light exposure it is equal.
The variation of the contact angle of SAM films in Excimer lamp reach stablize until during exposure be 75s × 8.25mW/cm2=618.25mJ/cm2.If the illumination conversion of wavelength 200nm below light of the VUV-SFL on SAM films as a result, For the illumination of Excimer lamp, then 75s/120s × 8.25mW/cm is equivalent to2=5.16mW/cm2。
I.e., it is believed that in the case where making above-mentioned VUV-SFL light with input energy 3.6J, 10Hz, if making quasi-molecule Lamp is with illumination 5.16mW/cm2It lights, then the exposure phase per unit time of the wavelength 200nm VUV lights below from the two Deng.
Therefore, it in ozone concentration determination experiment, is generated when having carried out to being lighted the 3.6J VUV-SFL inputted with 10Hz Ozone concentration and illumination is adjusted to 5.16mW/cm2Centre wavelength 172nm, ignition frequency 140kHz quasi-molecule The ozone concentration generated when lamp is lighted is measured and compares the experiment of the two.
Fig. 6 is the figure for indicating experimental system used in ozone concentration determination experiment.
Lamp 41 is above-mentioned Excimer lamp or VUV-SFL.The lamp 41 is housed in lampshade 42, the light discharged from the lamp 41 From the window portion 43 of the VUV permeabilities set on lampshade 42 to external irradiation.
In addition, the light exit side in lamp 41 configures the circulation chamber 44 being made of VUV permeability materials.From being formed in the circulation The open end 45 of one end of room 44 imports air to the inside of circulation chamber 44, and ozone instrument is connected in the other end of circulation chamber 44 46.The wall thickness of circulation chamber 44 is, for example, 1mm, and the sectional area in Fig. 6 is, for example, 3mm × 24mm.
As ozone instrument 46, weak former industry Co. Ltd. system " EG-2001RAH035 " has been used.The gas of ozone instrument 46 is taken out Pipette is 1.5 liters/min.
The aluminium foil of the opening 47a with 1cm × 1cm quadrangles is equipped on the photoirradiated surface of circulation chamber 44 as mask 47.That is, to the VUV irradiated areas of the air exposure flowed through in circulation chamber 44 be 1cm2.From the window portion 43 of lampshade 42 to mask M tables The gap length D in face is for example set as 2.5mm.
In addition, Fig. 6 is for easy understanding and turgidly to be described, magnitude relationship not necessarily reflects actual Experimental system.
In that above experimental system, as described above, determine when being lighted the 3.6J VUV-SFL inputted with 10Hz The ozone concentration of generation and the illumination for the chamber surface that circulates is adjusted to 5.16mW/cm2Centre wavelength 172nm, light frequency The ozone concentration that the Excimer lamp of rate 140kHz generates when lighting.It the results are shown in Fig. 7.
In the figure 7, solid line is the ozone concentration measurement result of VUV-SFL, and dotted line is that the ozone concentration of Excimer lamp measures As a result.
As shown in Fig. 7, it is respectively by VUV-SFL and the Excimer lamp ozone concentration lighted then after three minutes 0.64ppm、4.78ppm.In this way, despite lighted in a manner of keeping the exposure in the regions VUV identical Excimer lamp and VUV-SFL, but the ozone concentration of a side of VUV-SFL that pulse is lighted becomes smaller.That is, specifying when lighting in an atmosphere, pulse The ozone production quantity of a side of the VUV-SFL lighted becomes smaller.
In addition, in the case where lighting Excimer lamp, since lighting after about 30 seconds, ozone concentration reaches peak value, Ozone concentration gradually decreases later, it is believed that this is because from lamp is lighted and begun to pass through after 30 seconds, light temperature rises, quasi-molecule Enclosed gas temperature in light bulb rises, and the self-absorption for enclosing the lower quasi-molecule light of gas effect increases, as a result, comes from Excimer lamp VUV burst sizes gradually decrease.
The ignition frequency of Excimer lamp used herein be 140kHz, therefore as shown in figure 8, the Excimer lamp shine between Every T be 7 × 10-6Second.In addition, in fig. 8, horizontal axis is the time, the longitudinal axis is light output (arbitrary unit).In addition, LED pulse is wide The FWHM (full width at half maximum (FWHM)) for spending tp is about 2 μ s.Therefore, (=LED pulse width tp/'s luminous duty ratio of Excimer lamp shines Interval T) be
2×10-6/7×10-6=0.29 (29%).
On the other hand, due to the ignition frequency of VUV-SFL be 10Hz, the VUV-SFL shine between be divided into 0.1 second. In addition, the FWHM of LED pulse width is about 10 μ s.Therefore, the luminous duty ratio of VUV-SFL is
1×10-5/ 0.1=1 × 10-4(0.01%).
In this way, in Excimer lamp and VUV-SFL, luminous duty ratio is significantly different.Accordingly, despite so that VUV The identical mode of exposure in region has lighted Excimer lamp and VUV-SFL, but when VUV-SFL is lighted lights than Excimer lamp When small one of the reason of ozone concentration, thus it is speculated that the luminous duty ratio for both being is significantly different.
I.e., thus it is speculated that in the case that luminous duty ratio is small, it is difficult to cause excitation state oxygen atom O (1D：Excitation state), oxygen The ozone reaction of formation that the three-body collision of son and surrounding medium (nitrogen molecular etc.) is brought.
In order to verify above-mentioned it is assumed that being different from multiple lamps of above-mentioned lamp (Excimer lamp, VUV-SFL) using duty ratio, point The other yield to ozone concentration is investigated.In addition, above-mentioned Excimer lamp is known as lamp A, VUV-SFL is known as lamp D.
The lamp of ozone yield when having investigated luminous again is lamp B and lamp C below.
Lamp B is the Excimer lamp for the VUV for discharging centre wavelength 172nm, the spectrum point of spatial distribution and lamp A shown in FIG. 1 Cloth is identical.Ignition frequency is 20kHz, and the FWHM of LED pulse width is about 2 μ s.
Lamp B shine between be divided into 5 × 10-5Second, therefore the luminous duty ratio of lamp B is
2×10-6/5×10-5=0.04 (4%).
Lamp C is the VUV-SFL for discharging wavelength 200nm VUV lights below, the spectrum point of spatial distribution and lamp D shown in Fig. 2 Cloth is identical.Ignition frequency is 100Hz, and the FWHM of LED pulse width is about 10 μ s.
It is divided into 0.01 second between the shining of lamp C, therefore the luminous duty ratio of lamp C is
1×10-6/ 0.01=0.001 (0.1%).
In addition, here, the input energy put into lamp B and lamp C is had adjusted, so that the photograph of the VUV light of lamp B and lamp C The amount of penetrating is identical as above-mentioned lamp A and lamp D.
It is then determined by the ozone concentration generated after three minutes to lighting each lamp A~D, obtains table 1 Shown in result.
[table 1]
It is because the action of each lamp A~D is being lighted in addition, being set as the measuring point of ozone concentration after three minutes Three minutes substantially constant reasons later.
Fig. 9 is to indicate light emission duty ratio (duty) and the relationship of ozone concentration based on result shown in above-mentioned table 1 Figure.
According to the Fig. 9 it is found that in an atmosphere in the case of the pulsed light of light of the irradiation comprising the regions VUV, if the regions pair VUV Identical in the exposure of air, then luminous duty ratio is smaller, and the yield of ozone is fewer.
In addition, implementing SAM films (FAS13, Wako Pure Chemical Industries, Ltd. in an atmosphere respectively using each lamp A~D System) patterning.As a result, in the case where having used lamp A and lamp B, due to the oxygenolysis of the ozone and SAM films of generation Reaction, such as shown in Figure 12, expansion, the local defect of SAM films for producing the etched width for the degree that cannot ignore are this So-called ozone etches OE, cannot carry out good patterning.On the other hand, in the case where having used lamp C and lamp D, production Raw ozone concentration is smaller, therefore the oxidative decomposition of ozone and SAM films is small, such as shown in Figure 11, can carry out good Patterning.
It is able to confirm that moreover, having investigated the when of generating ozone concentration and the relationship of patterning precision, such as generates ozone concentration For 4ppm or more, then patterned deformation caused by ozone etching is notable.
As shown in figure 9, being 0.01 below in luminous duty ratio, it can reliably make generation ozone concentration ratio 4ppm is small.That is, using VUV light and in the case of by SAM film figures, by using lamp C and D (VUV-SFL) that arteries and veins Punching shines and luminous duty ratio is 0.01 light source below, can carry out high-precision patterning.
Therefore, in the present embodiment, using VUV light by SAM film figures, using pulsed illumination, simultaneously And luminous duty ratio is 0.01 or less and the flash lamp more than 0.Specifically, above-mentioned luminous duty ratio is set as 0.00001 or more and 0.01 or less.If duty ratio becomes smaller, luminous number is reduced per unit time, it is therefore desirable to be increased every Once luminous output.That is, it needs to increase the input electric power put into lamp, there is the capacitor of energy as defined in savings (not scheme Show) power supply enlargement.Here, make duty ratio lower limit be 0.00001 be because, if duty ratio be less than 0.00001, for Increase the output in primary shine, above-mentioned power supply 15 becomes quite large-scale and no longer practicality.
It is further preferred that luminous duty ratio is set as 0.0001 or more and 0.001 or less.Thereby, it is possible to above-mentioned lamp Ozone concentration, is fully decreased to the degree that there is no problem in practicality by C, that luminescent condition that can relatively easily realize of lamp D.
Figure 10 is indicated using VUV light and by the figure of the configuration example of the light irradiation device of SAM film figures.
Light irradiation device 100 has the vacuum-ultraviolet light light supply apparatus 10 of radiation VUV light.Vacuum-ultraviolet light light supply apparatus 10 Have flash lamp 11, parabolic mirror 12, lamp housing 13 and the window portion 14 set on lamp housing 13.
Flash lamp 11 is the VUV-SFL for example with structure shown in Fig. 3.That is, flash lamp 11 has the following structure：Have It the luminous tube 111a that is made of vacuum-ultraviolet light transmission material and is configured in luminous tube 111a and mutually opposed one To electrode 113a, 113b, the interelectrode distance of a pair of electrodes 113a, 113b is 12.5mm hereinafter, in luminous tube 111a It is sealed with the gas comprising xenon with enclosed gas pressure 3atm.
In addition, in Fig. 10, although being not particularly illustrated, vacuum-ultraviolet light light supply apparatus 10 has and has as shown in figure 3 The power supply of 15 identical structure of power supply.
Flash lamp 11 is by 31 drive control of control unit at (being, for example, here with duty ratio 0.00001 or more and 0.01 or less 0.001) pulsed illumination.That is, control unit 31 carries out drive control to the power supply of vacuum-ultraviolet light light supply apparatus 10, to flash lamp The rechargeable energy (3.6J) of capacitor that 11 inputs are charged with 600V, 20 μ F of capacity, makes the flash lamp 11 be lighted with 10Hz.
The VUV light discharged from flash lamp 11 is reflected by parabolic mirror 12 and becomes directional light, and from set on lamp housing 13 window portion 14 is emitted.Window portion 14 is for example by there is the synthetic quartz of high transmittance to be formed VUV light.In addition, window portion 14 also may be used To be better than the formation such as quartzy sapphire glass or calcirm-fluoride, magnesium fluoride by the transmitance of such as short wavelength.
The window portion 14 is airtightly assembled with lamp housing 13, is imported from the gas set on lamp housing 13 inside lamp housing 13 Mouth 13a imports nitrogen (N2) inert gases such as gas, oxygen (Purge) in the inside of the lamp housing 13 by inert gas removing.This is Because VUV is consumingly by the attenuation by absorption caused by oxygen, by with N2The inert gases such as gas are in lamp housing 13 It is purged, the attenuation by absorption caused by oxygen of VUV can be prevented.In addition, importeding into the inert gas inside lamp housing 13 After cooling down flash lamp 11, parabolic mirror 12, from the exhaust outlet 13b exhausts set on lamp housing 13.
In addition, for example can also be vacuum inside lamp housing 13.
The VUV light discharged from vacuum-ultraviolet light light supply apparatus 10 is incident on mask M.Mask M is, for example, by glass etc. The metals such as chromium are deposited on transparent substrate and are etched and form the mask of pattern (irradiation patterns), VUV light passes through mask M And it is irradiated to workpiece W.
It is equipped in the light exit side of vacuum-ultraviolet light light supply apparatus 10 and surrounds component 21, which will be from vacuum purple Outer radiant device 10 discharges and the light path advanced to the light of mask M incidences is surrounded.Mask M, which is fixed in, surrounds component 21 Mask platform 22 adsorbs holding with keeping horizontality.
The window portion 14 of vacuum-ultraviolet light light supply apparatus 10, the inside for surrounding component 21, mask platform 22 and mask M become envelope Close space.It surrounds component 21 and is equipped with gas introduction port 21a, from gas introduction port 21a to the encirclement component 21 as enclosure space Inside imports N2The inert gases such as gas remove oxygen inside the encirclement component 21 by inert gas.This is to be based on and lamp housing Oxygen inside body 13 removes identical reason by inert gas.In addition, importeding into the inert gas surrounded inside component 21 From set on the exhaust outlet 21b exhausts for surrounding component 21.
In addition, it for example can also be vacuum to surround inside component 21.
Workpiece W is positioned in work stage 23, such as is held in work stage 23 by the absorption of vacuum cup mechanism.In the workpiece It is formed with SAM films (SAM) on W, leaves about 100 μm or so away from mask M and configures.Moreover, being formed between workpiece W and mask M There is air layer.
Specifically, mask M light exit side be equipped with surround component 24, the encirclement component 24 will by mask M and to The light path that the light of workpiece W irradiation is advanced is surrounded, from the air induction port 24a that surrounds component 24 is formed in workpiece W and mask M Between import air.The air imported from air induction port 24a is vented from exhaust outlet 24b.In addition, between mask M and workpiece W It is not limited to air layer, as long as being formed with the oxygen containing gas blanket of packet.
In addition, work stage 23 be configured to by table transferring mechanism 32 to the directions XYZ θ (left and right of Figure 10, it is front and back, on Lower direction and the direction of rotation centered on Z axis) it is mobile.Table transferring mechanism 32 carries out drive control by control unit 31.
That is, carrying out the VUV treatment with irradiation of workpiece W as described below.
First, control unit 31 carries out drive control to vacuum cup mechanism etc., by vacuum suction to being placed in mask platform The mask M of 22 defined position is kept.Next, control unit 31 makes work stage 23 decline using table transferring mechanism 32, Workpiece W is set to be positioned in work stage 23.Later, control unit 31 makes work stage 23 rise using table transferring mechanism 32, and workpiece W is set It sets in defined VUV light irradiation position.Next, control unit 31 makes work stage 23 on the directions XY θ using table transferring mechanism 32 It is mobile, it is masked contrapositions (be aligned) of the M with workpiece W.That is, making pair of the alignment mark being imprinted on mask M on the workpiecew with print Fiducial mark note is consistent.
If mask M and the contraposition of workpiece W terminate, vacuum-ultraviolet light light supply apparatus 10 will shine as the VUV light of directional light It is mapped on mask M, carries out the photo-patterning processing of the SAM films on workpiece W.If photo-patterning processing terminates, 31 profit of control unit So that work stage 23 is declined with table transferring mechanism 32, stops, to 23 supply vacuum of work stage, becoming to take out from work stage 23 and shining Penetrate the state of the workpiece W of end.
As described above, in light irradiation device 100 in the present embodiment, preparation forms figuratum mask M, will cover Mould M and workpiece W is close and parallelly configures, and changes the partial illumination directional light of the characteristic of workpiece W by mask M only pair hope VUV light.In this way, the photo-patterning of workpiece W is handled.
At this point, light irradiation device 100 irradiates VUV light in air etc. wraps oxygen containing atmosphere to workpiece W.Therefore, to SAM When film has irradiated VUV light, the oxygen near SAM film surfaces becomes active oxygen by VUV irradiates, and can carry out VUV light to SAM films Direct decomposition, and the oxidative decomposition of the active oxygen and SAM films can also be carried out.As a result, with not comprising the lazy of oxygen Property gas atmosphere in compared like that, without the case where oxidative decomposition based on active oxygen to SAM films irradiation VUV, can Improve pattern rate (Patterning rate).
In addition, it is 0.01 light below that vacuum-ultraviolet light light supply apparatus 10, which discharges pulsed light and is luminous duty ratio, As the VUV light irradiated to workpiece W.The life of the ozone generated thereby, it is possible to inhibit the oxygen molecule in air atmosphere to absorb VUV Cheng Liang.In particular, by the way that above-mentioned luminous duty ratio is set as 0.0001 or more and 0.001 hereinafter, can be can be easier to The luminescent condition that ground is realized will generate ozone concentration and be substantially reduced to the degree that there is no problem in practicality.Therefore, it is possible to inhibit smelly Patterned deformation caused by oxygen etching, realizes good patterning.
Moreover, because using pulsed light and being that luminous duty ratio is answered for 0.01 light below as the light source of release For flash lamp 11, therefore it can suitably discharge the VUV light for meeting above-mentioned condition.
In addition, as flash lamp 11, it is 12.5mm or less and in luminous tube that can apply length of illumination (interelectrode distance) Inside it is sealed with the flash lamp of the gas comprising xenon.In this way, by using the light source for being considered as substantially point light source, light can be carried out The less exposure of diffraction.Therefore, it is possible to realize the miniaturization of pattern line-width.
(variation)
In the above-described embodiment, in the case where requiring to be irradiated to the uniformity of the Illumination Distribution of VUV light of workpiece W, Such as light irradiation device 100 can also be constituted as described below.
Parabolic mirror 12 in vacuum-ultraviolet light light supply apparatus 10 is set as oval condenser mirror, it is poly- in the ellipse The illumination region of the 1st focus configuration flash lamp 11 of light reflection mirror.In addition, the 2nd focus in the light optically focused discharged from window portion 14 is matched Integrator is set, so that the light from integrator is irradiated to mask M as directional light using collimation lens or collimating mirror.
Further, since integrator, collimation lens or collimating mirror are located at from the release of vacuum-ultraviolet light light supply apparatus 10 simultaneously It is irradiated in the light path that the light of workpiece W is advanced, therefore they need to be made of the good material of the translucency in the regions VUV, and They are also accommodated in the inside for surrounding component 21.
In addition, it is above-mentioned although the description of specific embodiment, but the embodiment only illustrates, and is not intended to limit this The range of invention.Device and method recorded in this specification can implement in mode than that described above.In addition, Also omission, replacement and change appropriate are carried out while the scope of the present invention can not departed to the above embodiment.It is somebody's turn to do The mode omitted, replace and changed is included in the range of the range recorded in claims and their equivalent, Belong to the technical scope of the present invention.
Industrial utilizability
Vacuum-ultraviolet light light supply apparatus according to the present invention can inhibit to discharge vacuum in air etc. wraps oxygen containing atmosphere The amount of the ozone generated when ultraviolet light, therefore be useful.In addition, in the light irradiation for being equipped with the vacuum-ultraviolet light light supply apparatus In device, in the patterned process of the SAM films in wrapping oxygen containing atmosphere, the oxidation of the ozone and SAM films that generate can be inhibited Ozone etching caused by decomposition reaction, so as to realize good patterning, therefore is useful.
Reference sign
10 ... vacuum-ultraviolet light light supply apparatus, 11 ... flash lamps (VUV-SFL), 12 ... parabolic mirrors, 13 ... lamp housings Body, 14 ... window portions, 15 ... power supplies, 21 ... encirclement components, 21a ... gas introduction ports, 21b ... exhaust outlets, 22 ... mask platforms, 23 ... work stages, 24 ... surround component, 24a ... air induction ports, 24b ... exhaust outlets, 31 ... control units, 32 ... platform moving machines Structure, 41 ... lamps, 42 ... lampshades, 43 ... window portions, 44 ... circulation chambers, 45 ... open ends, 46 ... ozone instrument, 47 ... masks, 47a ... are opened Mouthful, 111a ... luminous tubes, the first seal pipes of 111b ..., the second seal pipes of 111c ..., 112 ... glass for sealing pipes, 113a ... the One main electrode, the second main electrodes of 113b ..., 114a ... conducting wires, 114b ... conducting wires, 115a, 115b ... startup auxiliary electrode, 116a, 116b ... inner leads, 117a, 117b ... outer lead, 118a, 118b ... metal foil, 119 ... support elements, M ... masks, SAM ... self-assembled monolayers (SAM films), W ... workpiece.

Claims (7)

1. a kind of patterning apparatus of self-assembled monolayer includes true to the self-assembled monolayer irradiation being formed on workpiece The light of empty ultraviolet light, which is characterized in that have：
Mask discretely configures with the above-mentioned workpiece for being formed with above-mentioned self-assembled monolayer, is formed with defined pattern；
Light source irradiates the above-mentioned light for including vacuum-ultraviolet light via aforementioned mask on above-mentioned workpiece；And
Gas introduction part wraps oxygen containing gas to being imported between aforementioned mask and above-mentioned workpiece, is formed and wrap oxygen containing gas blanket,
The above-mentioned light comprising vacuum-ultraviolet light is pulsed light, and be luminous duty ratio is 0.00001 or more and 0.01 or less Light.
2. the patterning apparatus of self-assembled monolayer according to claim 1, which is characterized in that
Above-mentioned luminous duty ratio is 0.0001 or more and 0.001 or less.
3. the patterning apparatus of self-assembled monolayer according to claim 1 or 2, which is characterized in that have：
Flash lamp has the luminous tube being made of vacuum-ultraviolet light transmission material and configures mutual in the luminous tube Opposed pairs electrode；And
Power supply is supplied electric power to above-mentioned flash lamp.
4. the patterning apparatus of self-assembled monolayer according to claim 3, which is characterized in that
The interelectrode distance of above-mentioned a pair of electrodes of above-mentioned flash lamp is 12.5mm hereinafter, being sealed in above-mentioned luminous tube and including The gas of xenon.
5. a kind of light irradiation device, which is characterized in that have：
Mask discretely configures with the workpiece for being formed with self-assembled monolayer, is formed with defined pattern；
Vacuum-ultraviolet light light supply apparatus irradiates the light for including vacuum-ultraviolet light via aforementioned mask on above-mentioned workpiece；And
Component is surrounded, the light path of the above-mentioned light from above-mentioned vacuum-ultraviolet light light supply apparatus to aforementioned mask is surrounded；
The above-mentioned light comprising vacuum-ultraviolet light is pulsed light, and be luminous duty ratio is 0.00001 or more and 0.01 or less Light,
The inside of above-mentioned encirclement component is cleaned by inert gas,
The oxygen containing gas blanket of packet is formed between aforementioned mask and above-mentioned workpiece.
6. a kind of patterning method of self-assembled monolayer, via the mask for being formed with defined pattern, to being formed in workpiece On self-assembled monolayer irradiation include the light of vacuum-ultraviolet light, which is characterized in that
In wrapping oxygen containing atmosphere, as the above-mentioned light for including vacuum-ultraviolet light, irradiating pulsed light and be luminous duty ratio For 0.00001 or more and 0.01 light below.
7. the patterning method of self-assembled monolayer according to claim 6, which is characterized in that
As the above-mentioned light for including vacuum-ultraviolet light, it is 0.0001 or more and 0.001 below to irradiate above-mentioned luminous duty ratio Light.
CN201580038998.7A 2014-07-17 2015-07-09 The patterning apparatus of self-assembled monolayer, the patterning method of light irradiation device and self-assembled monolayer Active CN106537553B (en)

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PCT/JP2015/003467 WO2016009624A1 (en) 2014-07-17 2015-07-09 Vacuum ultraviolet light source device, light irradiation device and method for patterning self-assembled monomolecular film

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